CN107910576A - The preparation method of the anionic polymer film of a kind of high chemical stability - Google Patents
The preparation method of the anionic polymer film of a kind of high chemical stability Download PDFInfo
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- CN107910576A CN107910576A CN201711071270.1A CN201711071270A CN107910576A CN 107910576 A CN107910576 A CN 107910576A CN 201711071270 A CN201711071270 A CN 201711071270A CN 107910576 A CN107910576 A CN 107910576A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1086—After-treatment of the membrane other than by polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/124—Copolymers alternating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3221—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses the preparation method of the anionic polymer film of a kind of high chemical stability, belong to ionic polymer membranes field.Under the catalysis of mixing super acids, addition condensation reaction occurs for aryl compound and 4 piperidines ketone compounds of N alkyl, obtains that molecular weight is big and the linear macromolecule of narrow molecular weight distribution.The nitrogen heterocyclic ring on polymer chain is carried out with iodomethane or brominated alkanes quaternised modified, obtained quaternized ionomer is immersed in dense strong base solution and carries out ion exchange, washing and drying, finally dissolves casting film by obtained ionomer.Experimentation of the present invention is succinct, efficient, and obtained anionic polymer film has high ionic conductivity and ion exchange capacity, and chemistry, heat endurance and mechanical strength are very excellent.The invention has good application prospect and potentiality to be exploited in alkaline polymer fuel cell field.There is very big advantage than the anionic polymer film being used at this stage in fuel cell.
Description
Technical field
The invention belongs to ionic polymer membranes field, is related to the preparation of the anionic polymer film of a kind of high chemical stability
Method.
Background technology
In recent years, fuel cell technology development is swift and violent, and particularly Proton Exchange Membrane Fuel Cells technology has been applied to car
Carry dynamical system.Toyota Motor company was proposed the battery that a brand-new fuel-cell vehicle Mirai is used in 2014
Technology is exactly Proton Exchange Membrane Fuel Cells technology.But this types of fuel cells is dependent on noble metal catalyst and costliness
Nafion proton exchange membrane, its development space are extremely limited.In contrast, alkaline polymer electrolyte fuel cell has
There is great advantage.It can both break away from the dependence to noble metal, the preparation of anionic polymer film be also dirt cheap with it is various.And
And applied in actual alkaline polymer electrolyte fuel cell.(S.Lu,J.Pan,A.Huang,
L.Zhuang.Proc.Natl.Acad.Sci.U.S.A.,2008,105,20611–20614.).But with alkaline polymer
The development of electrolyte fuel battery technology, people are gradually, it is realized that except anionic polymer film to be improved is in alkaline polymer
Outside battery performance in electrolyte fuel battery, chemical stability of the anionic polymer film under strong basicity environment is improved
Very crucial, good chemical stability is the guarantee of fuel cell long-time stable work.So researching and developing high performance the moon
While ionic polymer membranes, the problem of chemical stability of anionic polymer film is also paid close attention to the most into researchers it
One.(M.G.Marino,K.D.Kreuer.ChemSusChem.2014,7,1–12.).Exploitation is a kind of have high chemical stability,
The anionic polymer film of high thermal stability, high mechanical properties, becomes the one of the development of alkaline polymer electrolyte fuel cell
Big challenge.
The content of the invention
For above-mentioned challenge, the present invention is in order to improve the chemical stability of anionic polymer film, it is proposed that a kind of new
Anionic polymer film preparation method, and obtained that a kind of ion exchange capacity is high, and electrical conductivity is good, and heat endurance is good,
Mechanical strength is excellent and possesses the anionic polymer film for having fabulous chemical stability, this anionoid polymer film is one
Class is very potential, can apply to alkaline polymer electrolyte fuel cell barrier film material.
The preparation method of the present invention includes the following steps：
The preparation method of the anionic polymer film of a kind of high chemical stability, its preparation process are as follows：
1) synthesis of polymer：Using the mixed acid of trifluoromethanesulfonic acid and trifluoroacetic acid as catalyst, with aryl compound and
N- alkyl -4- piperidines ketone compounds are reaction monomers, make the addition condensation that nucleophilic occurs in the first solvent for reaction monomers anti-
Should, obtain initial polymer；
2) polymer is quaternized：The initial polymer that step 1) is obtained be dissolved in the second solvent obtain it is uniform molten
Liquid, adds excessive quaternizing agent iodomethane or brominated alkanes, when reaction 3~24 is small between 40~75 DEG C, will react
Solution afterwards, which is poured into ether, to be precipitated, and precipitation is repeatedly washed with ether, obtains quaternized ionomer；
3) ion exchange of ionomer：Ionomer quaternized obtained by step 2) is immersed in 1mol/L's
In KOH or NaOH solution, stirred at 50 DEG C to 60 DEG C 12~36 it is small when, then by obtained solid centrifuge washing 6~10 times to filtering
Liquid is neutrality, and when drying 24~48 is small in 60~100 DEG C of vacuum drying chambers, it is OH to obtain anion-Ionomer；
4) form a film：Ionomer obtained by step 3) is dissolved in dimethyl sulfoxide (DMSO), casting on a glass, 60~
Dried in 100 DEG C of baking ovens, obtain OH-The anionic polymer film of type.
Preferably, the molar ratio of the aryl compound and N- alkyl -4- piperidines ketone compounds is 1:1~1:1.1；
Trifluoromethanesulfonic acid and the volume ratio of trifluoroacetic acid are 12 in the mixed acid:1~25:1；The body of first solvent and mixed acid
Product is than being 0~0.25：1；Molar concentration of the aryl compound in mixed acid is 0.98~1.37mol/L.
Preferably, the aryl compound include biphenyl, para-terpheny, meta-terphenyl, to quaterphenyl, 4,4 '-hexichol oxygen
Base Benzophenone；N- alkyl -4- piperidines ketone compounds include N- methyl -4- piperidones, N- ethyl -4- piperidones, N- propyl group -4
Piperidones.
Preferably, the first solvent described in step 1) is any of dichloromethane, 1,2- dichloroethanes, chloroform.
Preferably, in step 2), the concentration of initial polymer is 33.3mg/mL~66.7mg/mL；Quaternizing agent with just
The molar ratio of beginning constitutional unit is 18:1~25:1.
Preferably, the second solvent described in step 2) is -2 pyrrolidones of 1- methyl, or -2 pyrrolidones of 1- methyl with
The mixed solvent of dimethyl sulfoxide.
Preferably, brominated alkanes described in step 2) include bromoethane, N-Propyl Bromide, bromo n-hexane, bromocyclohexane.
The anionic polymer film of a kind of high chemical stability, adopts and is prepared with the aforedescribed process.
The synthetic route of the anionic polymer film of one kind high chemical stability of the invention is as follows：
Anionic polymer film prepared by the present invention is applied in alkaline fuel cell, can obtain very high ion exchange
Capacity and ionic conductivity.Its conductivity at room temperature can reach 60mS/cm during ion exchange capacity 2.50mmol/g, 80 DEG C
Ionic conductivity can even reach 180mS/cm.And this kind of film has considerable mechanical strength, what is be humidified completely
In the case of the tensile strength of room temperature reach 38.9MPa, elongation at break 37.8%, the anion of this kind of excellent combination property gathers
Compound film, which is applied to alkaline polymer fuel cell, has very big advantage.In addition, this kind of anionic polymer film has
Extraordinary chemical stability.After being soaked in 80 DEG C of NaOH solutions of 2mol/L to 10mol/L various concentrations 10 days still
Keep higher ion concentration.Particularly when NaOH solution is at concentrations up to 4mol/L, quaternary ammonium cation only degrades
4.6%.This good mechanical strength and high chemical stability make it be expected to very much alkaline polymer electrolyte can be applied to fire
Expect battery, improve the stability of battery.
Brief description of the drawings
Fig. 1 is that the anionic polymer film of the embodiment of the present invention 1 soaks in 80 DEG C of NaOH solutions of 2-10M various concentrations
The nuclear-magnetism results contrast of film of the nuclear-magnetism result with not soaking NaOH after 10 days；
Fig. 2 is that the anionic polymer film of the embodiment of the present invention 1 soaks in 80 DEG C of NaOH solutions of 2-10M various concentrations
The remaining situation of ion after 10 days.
Embodiment
Below by specific embodiment, the present invention is further illustrated, and its object is to help to be better understood from this hair
Bright content, but these specific embodiments are not in any way limit the scope of the present invention.Used in the present embodiment
Raw material is common known compound, is commercially available.
Embodiment 1
The biphenyl of 41.0mmol is weighed in 150mL three-necked flasks, the 1- methyl -4- piperidones of 42.0mmol is added, adds
Enter 8.6mL dichloromethane dissolving reactant.The trifluoromethanesulfonic acid of 32mL and mixing for trifluoroacetic acid are added under conditions of ice-water bath
Acid is closed, both volume ratios are 15:1, when reaction 3 is small.Product precipitates in solution of potassium carbonate, and is fully washed with deionized water,
When drying 24 is small in 60-80 DEG C of baking oven.Obtain initial polymerization raw material.
Weigh the above-mentioned polymer of 10.0mmol and add in 1-Methyl-2-Pyrrolidone and dissolve, be made into mass fraction as 33.3
The polymer solution of~66.7mg/mL, adding the iodomethane of 18.5~20 times of equivalents, that 8-16 is reacted under the conditions of 40-60 DEG C is small
When, obtain the quaternized polymer of differential responses efficiency.Precipitation obtains the powdered solid of yellow in ether after the completion of reaction
Body, precipitation is washed with ether repeatedly.Obtain quaternized ionomer.
By ionomer obtained above be immersed in 60 DEG C of 1mol/L KOH solutions 24 it is small when, iodide ion is abundant
It is exchanged into hydroxide ion.Afterwards by solid centrifuge washing for several times until clear liquid is neutrality.Gained white solid is at 60-100 DEG C
When drying 24-48 is small in baking oven, white powdery solids are obtained.Above-mentioned solid is dissolved in dimethyl sulfoxide, casts in glass
On plate, dried in 60-100 DEG C of baking oven, obtain OH-The anionic polymer film of type.
The synthesis solvent for use of polymer changes 1,2- dichloroethanes into this example, and chloroform does not interfere with follow-up result.
Ionic conductivity and ion exchange capacity (IEC) test are carried out to anionic polymer film obtained by the present embodiment, from
Electron conductivity measurement is measured with Metrohm Autolab electrochemical test systems, using two electrode AC impedance methods, measurement
The ionic conductivity of the anionic polymer film of full hygrometric state.Ion exchange capacity (IEC) is by silver nitrate titration chlorion
Precipitation titration, titrates out the anion-content in certain mass anionic polymer film, so as to obtain anionic polymer film
IEC.Measurement result shows, anionic polymer film prepared by the present invention, can obtain very high ion exchange capacity and from
Electron conductivity, its room temperature OH during ion exchange capacity 2.50mmol/g-Ionic conductivity can reach 60mS/cm, at 80 DEG C from
Electron conductivity reaches 180mS/cm.
Anionic polymer film obtained by the present embodiment is placed in 80 DEG C, is soaked 10 days in the NaOH solution of 2~10mol/L,
Then nuclear-magnetism characterization is carried out to film and cation residue situation is calculated by nuclear-magnetism result.Fig. 1 be soaked the film of NaOH with not
The nuclear-magnetism results contrast of the film of NaOH is soaked, Fig. 2 is cation after gained film soaks 10 days in various concentrations NaOH solution
Remaining situation.It can be seen that after being soaked 10 days in 80 DEG C of NaOH solutions of 2mol/L to 10mol/L various concentrations
Still maintain higher ion concentration.Particularly when NaOH solution is at concentrations up to 4mol/L, quaternary ammonium cation only degrades
4.6%, this high chemical stability makes it be expected to be used for very much alkaline polymer electrolyte fuel cell.
Embodiment 2
Initial polymerization raw material is synthesized according to the method for embodiment 1.
Weigh and dissolved in the initial polymerization raw material addition 1-Methyl-2-Pyrrolidone of 10.0mmol, be made into mass fraction
For the polymer solution of 33.3~66.7mg/mL, the bromoethane of 30~35 times of equivalents is added when 70~75 DEG C of reactions 24 are small.Instead
Precipitation obtains albescent pulverulent solids in ether after the completion of answering, and washs precipitation repeatedly with ether.Obtain it is quaternized from
Sub- polymer.
By ionomer obtained above be immersed in 60 DEG C of 1mol/L KOH solutions 24 it is small when, bromide ion is abundant
It is exchanged into hydroxide ion.Afterwards by solid centrifuge washing for several times until clear liquid is neutrality.Gained white solid is at 60-100 DEG C
When drying 24-48 is small in baking oven, white powdery solids are obtained.Above-mentioned solid is dissolved in dimethyl sulfoxide, casts in glass
On plate, dried in 60-100 DEG C of baking oven, obtain OH-The anionic polymer film of type.
Use N-Propyl Bromide in this example, 1- bromine normal butanes, 1- bromine pentanes, 1- bromine n-hexanes, bromocyclohexane etc. replaces bromine
Ethane can also obtain the anionic polymer film of similarity.
Embodiment 3
The biphenyl of 41.0mmol is weighed in 150mL three-necked flasks, the 1- ethyl -4- piperidones of 43.0mmol is added, adds
Enter 8.0mL dichloromethane dissolving reactant.The trifluoromethanesulfonic acid of 32mL and mixing for trifluoroacetic acid are added under conditions of ice-water bath
Acid is closed, both volume ratios are 15:1, when reaction 2 is small.Product precipitates in solution of potassium carbonate, and is fully washed with deionized water,
When drying 24 is small in 60-80 DEG C of baking oven.Obtain initial polymerization raw material.
Weigh the above-mentioned polymer of 10.0mmol and add in 1-Methyl-2-Pyrrolidone and dissolve, be made into mass fraction as 33.3
The polymer solution of~66.7mg/mL, adding the iodomethane of 20~22 times of equivalents, that 20-30 is reacted under the conditions of 70~75 DEG C is small
When, obtain the quaternized polymer of differential responses efficiency.Precipitation obtains the powdered solid of yellow in ether after the completion of reaction
Body, precipitation is washed with ether repeatedly.Obtain quaternized ionomer.
By ionomer obtained above be immersed in 60 DEG C of 1mol/L KOH solutions 24 it is small when, iodide ion is abundant
It is exchanged into hydroxide ion.Afterwards by solid centrifuge washing for several times until clear liquid is neutrality.Gained white solid is at 60-100 DEG C
When drying 24-48 is small in baking oven, white powdery solids are obtained.Above-mentioned solid is dissolved in dimethyl sulfoxide, casts in glass
On plate, dried in 60-100 DEG C of baking oven, obtain OH-The anionic polymer film of type.
The synthesis solvent for use of polymer changes 1,2- dichloroethanes into this example, and chloroform does not interfere with follow-up result.
Embodiment 4
The biphenyl of 41.0mmol is weighed in 150mL three-necked flasks, the 1- propyl group -4- piperidones of 41.0mmol is added, adds
Enter 8.0mL dichloromethane dissolving reactant.The trifluoromethanesulfonic acid of 32mL and mixing for trifluoroacetic acid are added under conditions of ice-water bath
Acid is closed, both volume ratios are 16:1, when reaction 2 is small.Product precipitates in solution of potassium carbonate, and is fully washed with deionized water,
When drying 24 is small in 60-80 DEG C of baking oven.Obtain initial polymerization raw material.
Weigh the above-mentioned polymer of 10.0mmol and add 1-Methyl-2-Pyrrolidone dissolving, be made into mass fraction for 33.3~
The polymer solution of 66.7mg/mL, adds the iodomethane of 20~25 times of equivalents when reaction 24-30 is small under the conditions of 75 DEG C, obtains
The quaternized polymer of differential responses efficiency.Precipitation obtains the pulverulent solids of yellow in ether after the completion of reaction, uses second
Ether washs precipitation repeatedly.Obtain quaternized ionomer.
By ionomer obtained above be immersed in 60 DEG C of 1mol/L KOH solutions 24 it is small when, iodide ion is abundant
It is exchanged into hydroxide ion.Afterwards by solid centrifuge washing for several times until clear liquid is neutrality.Gained white solid is at 60-100 DEG C
When drying 24-48 is small in baking oven, white powdery solids are obtained.Above-mentioned solid is dissolved in dimethyl sulfoxide, casts in glass
On plate, dried in 60-100 DEG C of baking oven, obtain OH-The anionic polymer film of type.
The synthesis solvent for use of polymer changes 1,2- dichloroethanes into this example, and chloroform does not interfere with follow-up result.
Embodiment 5
The para-terpheny of 10.8mmol is weighed in 150mL three-necked flasks, adds the 1- methyl -4- piperidines of 10.8mmol
Ketone, adds 4.0mL dichloromethane dissolving reactant.The trifluoromethanesulfonic acid and trifluoroacetic acid of 11mL is added under conditions of ice-water bath
Mixed acid, both volume ratios be 25:2, when reaction 5 is small.Product precipitates in solution of potassium carbonate, and is fully washed with deionized water
Wash, when drying 24 is small in 60-80 DEG C of baking oven.Obtain initial polymerization raw material.
It is 5 to weigh the above-mentioned polymer of 10.0mmol and add volume ratio:1 1-Methyl-2-Pyrrolidone and dimethyl sulfoxide
In the mixed solvent dissolves, and is made into the polymer solution that mass fraction is 33.3~66.7mg/mL, adds the iodine of 20~25 times of equivalents
Methane obtains the quaternized polymer of differential responses efficiency when reaction 20-30 is small under the conditions of 55~65 DEG C.After the completion of reaction
Precipitation obtains the pulverulent solids of yellow in ether, washs precipitation repeatedly with ether.Obtain quaternized ionomer.
By ionomer obtained above be immersed in 60 DEG C of 1mol/L KOH solutions 24 it is small when, iodide ion is abundant
It is exchanged into hydroxide ion.Afterwards by solid centrifuge washing for several times until clear liquid is neutrality.Gained white solid is at 60-100 DEG C
When drying 24-48 is small in baking oven, white powdery solids are obtained.Above-mentioned solid is dissolved in dimethyl sulfoxide, casts in glass
On plate, dried in 60-100 DEG C of baking oven, obtain OH-The anionic polymer film of type.
Tensile strength test is carried out to the present embodiment resulting polymers film, under conditions of full hygrometric state, it is 5* to cut size
The polymer film of 1cm sizes, in the tensile strength and elongation at break of tension test airborne measurements film.Obtain this kind of membrane material tool
There are the up to tensile strength of 38.9MPa, and 37.8% elongation at break.It is considerable to illustrate that this kind of polymer film has
Mechanical strength.Good mechanical strength can make it remain good during alkaline polymer electrolyte fuel cell test
Good dimensional stability, improves stability test.
Embodiment 6
The meta-terphenyl of 10.8mmol is weighed in 150mL three-necked flasks, adds the 1- methyl -4- piperidines of 10.8mmol
Ketone, adds 4.0mL dichloromethane dissolving reactant.The trifluoromethanesulfonic acid and trifluoroacetic acid of 11mL is added under conditions of ice-water bath
Mixed acid, both volume ratios be 25:2, when reaction 5 is small.Product precipitates in solution of potassium carbonate, and is fully washed with deionized water
Wash, when drying 24 is small in 60-80 DEG C of baking oven.Obtain initial polymerization raw material.
It is 5 to weigh the above-mentioned polymer of 10.0mmol and add volume ratio:1 1-Methyl-2-Pyrrolidone and dimethyl sulfoxide
In the mixed solvent dissolves, and is made into the polymer solution that mass fraction is 33.3~66.7mg/mL, adds the iodine of 20~25 times of equivalents
Methane obtains the quaternized polymer of differential responses efficiency when reaction 20-30 is small under the conditions of 55~65 DEG C.After the completion of reaction
Precipitation obtains the pulverulent solids of yellow in ether, washs precipitation repeatedly with ether.Obtain quaternized ionomer.
By ionomer obtained above be immersed in 60 DEG C of 1mol/L KOH solutions 24 it is small when, iodide ion is abundant
It is exchanged into hydroxide ion.Afterwards by solid centrifuge washing for several times until clear liquid is neutrality.Gained white solid is at 60-100 DEG C
When drying 24-48 is small in baking oven, white powdery solids are obtained.Above-mentioned solid is dissolved in dimethyl sulfoxide, casts in glass
On plate, dried in 60-100 DEG C of baking oven, obtain OH-The anionic polymer film of type.
Embodiment 7
The 4 of 11.7mmol are weighed, 4 '-two phenoxy group Benzophenones add the 1- first of 11.7mmol in 150mL three-necked flasks
Base -4- piperidones, adds the trifluoromethanesulfonic acid of 13.0mL and the mixed acid of trifluoroacetic acid, both volumes under conditions of ice-water bath
Than for 40:3, when reaction 6 is small.Product precipitates in solution of potassium carbonate, and is fully washed with deionized water, in 60-80 DEG C of baking oven
When middle drying 24 is small.Obtain initial polymerization raw material.
It is 5 to weigh the above-mentioned polymer of 10.0mmol and add volume ratio:1 1-Methyl-2-Pyrrolidone and dimethyl sulfoxide
In the mixed solvent dissolves, and is made into the polymer solution that mass fraction is 33.3~66.7mg/mL, adds the iodine of 20~25 times of equivalents
Methane obtains the quaternized polymer of differential responses efficiency when reaction 20-24 is small under the conditions of 60~70 DEG C.After the completion of reaction
Precipitation obtains the pulverulent solids of yellow in ether, washs precipitation repeatedly with ether.Obtain quaternized ionomer.
By ionomer obtained above be immersed in 60 DEG C of 1mol/L KOH solutions 24 it is small when, iodide ion is abundant
It is exchanged into hydroxide ion.Afterwards by solid centrifuge washing for several times until clear liquid is neutrality.Gained white solid is at 60-100 DEG C
When drying 24-48 is small in baking oven, white powdery solids are obtained.Above-mentioned solid is dissolved in dimethyl sulfoxide, casts in glass
On plate, dried in 60-100 DEG C of baking oven, obtain OH-The anionic polymer film of type.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than the present invention is protected
The limitation of scope is protected, although being explained in detail with reference to preferred embodiment to the present invention, those of ordinary skill in the art should
Understand, can be to technical scheme technical scheme is modified or replaced equivalently, without departing from the essence of technical solution of the present invention
And scope.
Claims (8)
1. the preparation method of the anionic polymer film of a kind of high chemical stability, it is characterised in that its preparation process is as follows：
1) synthesis of polymer：Using the mixed acid of trifluoromethanesulfonic acid and trifluoroacetic acid as catalyst, with aryl compound and N- alkane
Base -4- piperidines ketone compounds are reaction monomers, make reaction monomers that the addition condensation reaction of nucleophilic occur in the first solvent, obtain
To initial polymer；
2) polymer is quaternized：The initial polymer that step 1) is obtained, which is dissolved in the second solvent, obtains uniform solution,
Excessive quaternizing agent iodomethane or brominated alkanes are added, when reaction 3~24 is small between 40~75 DEG C, after reaction
Solution is poured into ether and precipitated, and precipitation is repeatedly washed with ether, obtains quaternized ionomer；
3) ion exchange of ionomer：By quaternized ionomer obtained by step 2) be immersed in 1mol/L KOH or
In NaOH solution, stir at 50 DEG C to 60 DEG C 12~36 it is small when, then be to filtrate for 6~10 times by obtained solid centrifuge washing
Property, when drying 24~48 is small in 60~100 DEG C of vacuum drying chambers, it is OH to obtain anion-Ionomer；
4) form a film：Ionomer obtained by step 3) is dissolved in dimethyl sulfoxide (DMSO), is cast on a glass, 60~100
Dried in DEG C baking oven, obtain OH-The anionic polymer film of type.
2. the preparation method of the anionic polymer film of a kind of high chemical stability according to claim 1, it is characterised in that
The molar ratio of the aryl compound and N- alkyl -4- piperidines ketone compounds is 1:1~1:1.1；Three in the mixed acid
The volume ratio of fluorine methanesulfonic acid and trifluoroacetic acid is 12:1~25:1；The volume ratio of first solvent and mixed acid is 0~0.25：
1；Molar concentration of the aryl compound in mixed acid be：0.98~1.37mol/L.
3. the preparation method of the anionic polymer film of a kind of high chemical stability according to claim 1, it is characterised in that
The aryl compound include biphenyl, para-terpheny, meta-terphenyl, to quaterphenyl, 4,4 '-two phenoxy group Benzophenones；N- alkyl-
4- piperidines ketone compounds include N- methyl -4- piperidones, N- ethyl -4- piperidones, -4 piperidones of N- propyl group.
4. the preparation method of the anionic polymer film of a kind of high chemical stability according to claim 1, it is characterised in that
The first solvent described in step 1) is any of dichloromethane, 1,2- dichloroethanes, chloroform.
5. the preparation method of the anionic polymer film of a kind of high chemical stability according to claim 1, it is characterised in that
In step 2), the concentration of initial polymer is 33.3mg/mL~66.7mg/mL；Quaternizing agent and initial polymer structure list
The molar ratio of member is 18:1~25:1.
6. the preparation method of the anionic polymer film of a kind of high chemical stability according to claim 1, it is characterised in that
Second solvent described in step 2) is -2 pyrrolidones of 1- methyl, or the mixing of -2 pyrrolidones of 1- methyl and dimethyl sulfoxide is molten
Agent.
7. the preparation method of the anionic polymer film of a kind of high chemical stability according to claim 1, it is characterised in that
Brominated alkanes described in step 2) include bromoethane, N-Propyl Bromide, bromo n-hexane, bromocyclohexane.
8. the anionic polymer film of a kind of high chemical stability, it is characterised in that using any one of the claims 1-7 institutes
The method stated is prepared.
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